Phenol ether resins



Patented Aug. 18, 1953 r UNITED STATES PATENT OFFICE 2349,43?

V Li and Lewisa Shelton; Was si ndrs to Rayo iera n1: .no a Shelton, 'Wash., a corporation of Delaware Drawing. Application April 24', 1951,

Serial No. 222,734

6 Claims. (Cl. 26047) groupand R1 represents methyl or ethyl. Examples' of R include the following This invention relates toorg and resinous products an d has to M provision of w c a sfii ,di ldehys es. and hydric alcohols and a new; type otthermosetting resins prepared therefrom as well as methods of 5 vention provides an 'efiicient and economically v .7

advantageous method 'o f producingi the dialde: One important aspect of the invention isthat hydes and dihydric alcohols. Whilethesje .GQIII- the i starting materials for the dialdehydes and.

pounds have general utility; they are especially dihydric alcohols inay'be vanillin which is potenimportant in forming the-resins of the invention. tiall 'yv available "in great abundance by the alka- The so-called thermosettin'gFiresins-are charac-' line oxidation of sulfite waste liquor, a lay-product terized by a cross-linkedorlattice structure and intheman'ufacture of cellulosefrom wood.

have the property of being-infusibleand. insolu-jj Specific dialdehydes and dihydric alcohols may ble in all solvents except 'thosethat. decompose be prepared from vanillin by a series of reactions them. While the thermosetting resins heretofore as followsi CF1 v v one zNaBr 211,0

(2)- OCH: CHaO a more, OOH- oomomo 0H0 zomonon-olm oom CHaO "oomomo OHZOH met-(Loire produced are variously ecite H Reaction- 1' results in" the formation. of the molded resins of the'inventiofi'are colorless and" 3 diald'ehyde ethyle'ne divanillin ether which is an clear. V I V 5 important"intermediate in the method of this The dialdehydes and dihydric alco invention; invention are represented by theiollowingstrue- Reaction'2 results in theformation of the ditures: N hydric 'alcohol': hich, on condensation, forms o there'sins ofthe invention. I o 40 The resins -0f the present'invention are pre- C GC'E pared from dihydric alcohols of the following v structure:

0R1 R10 7 t I v I I HO CHPO-O R O QOHZOH In the above formulae, the R-grouprepresents 'Iflise confounds, condense int'ermolecularly a divalent aliphatic chain of2-4 earbonatoihs'" wheiighea te o'f 'forrin polymer by splitting" ut which maybe interrupted by an oxygen-ether waterbetween'the hydroxyl'groupsand'nuclear hydrogen atoms of an adjacent molecule, as illustrated in the following reaction:

on3 onto uct separated on cooling the reaction mixture. The product was crystallized from 250 parts of OCHs CHaO OCH:

OCH; CHsU CH... HOCHFOWOQaW l to The preparation of compounds of this inven- 7 tion is illustrated by the following specific examples:

Example 1.-Etheylene diva'm'llin ether OH: 01330 OOH ocmomo- CHO A mixture of 76 parts of vanillin, 21.2 parts of sodium hydroxide, 450 parts of water, and 47 parts of ethylene dibromide was placed in a reaction Vessel equipped with a mechanical stirring device and a reflux condenser. The mixture was heated to refluxing and stirred continuously for 21 hours. At the end of this time a tan-colored granular solid had separated from the. reaction mixture. This product. when dried had a melting point of l80184 C. The yield was 67.9 parts. It could be crystallized from the monomethyl ether of ethylene glycol to give colorless needles with no change in melting point. The product was ethylene divanillin ether,

Escample 2.--Ethyl'ene d'iiiam'llz'n ether A mixture of '76 parts of vanillin, 21.2 parts of sodium hydroxide, 450 parts of water, and 30 parts an equal mixture of ethyl alcohol and water. Twenty-five parts of crystalline product was obtained with a melting point of 115-l25 C. The product was diethylene glycol divanillin ether.

Example 5. -Ethylene-bz's-(2-methoazy-4-hydroxymethylphenyl) ether 7 QQHs 0113(1) .GOOH.CH.O CH.OH

'A mixture of 35 parts of ethylene divanillin ether as prepared in Example 1, 403 parts of methyl isobutyl carbinol, and 15 parts of aluminum isopropoxide was placed in a distilling apparatus equipped with mechanical stirrer and a distilling column packed with glass helices and attached to a total reflux distillin head. The mixture was stirred and refluxed, and the distillate was bled off slowly. The vapor temperature was. 81 C". at the start and 13.5 parts of distillate was obtained at a vapor temperature of 81-90 C. This represents the isopropanol obtained from the aluminum isopropoxide. The vapor temperature then rose to 115 C. and 88 parts of distillate was obtained at a temperature of 1l5-127 C.

Boon

. This fraction contained methyl isobutyl keton of ethylene dichloride was placed in an autoclave V equipped with a mechanical stirrer. The mixture was heated to 120 130? C. and stirred continuously for 4 hours. The gauge pressure was 7 0 pounds at the start and fell to pounds at the end. A product similar to that of Example 1 was obtained in a yield of 46 parts.

Example 3.Tetram e th ylene divanillin ether cont 0113c oon-QocmomomcmoQ Example 4.Diethylene glycol divanz'llin ether cons CH3? 0 era-Q0 omomoomomoOono A mixture of 76 parts of vanillin, 20 parts of sodium hydroxide, 450 parts of water, and 38 parts of ,8,fi'-dichlorodiethyl ether was placed in a reaction vessel equipped with mechanical stirrer and stirred 18 hours at 99 C. A crystalline prodobtained from the oxidation of methyl isobutyl carbinol. The total refluxing time was 7 hours. The reaction mixture was then placed in a steam distillation apparatus and subjected to steam distillation until allthe. methyl isobutyl carbinol had been removed. The insoluble residue was then crystallized from water to give 27 parts of colorless, crystalline needles having a melting point of 132-l35 C. This product was ethylenebis-(2-methoxy-4-hydroxymethylphenyl) ether.

Example 6.Tetramethylene-bis- (2-methor' -4- [L droxymethylphenyl) ether OOHa CH3? O0 cmomcmcmoO-cmoh Example 7 .Bis-'- (2-methoxy-el-hydroxymethylphenoryethyl) ether H0 OHZ-OOCHZCH2OCHQCHlOO-C 1120 H This compound was prepared by the procedure HOCH 5 described in Exampl'e 5, using 12.8 parts of 'diethylene glycol divanillin ether, 5 parts 'of aluminum isopropoxide; and 250 parts 'of methyl. isobutyl carbinol. The product was crystallized from water. The melting po'int was 953 102 C. Example 8.Condensatin of ethylene bis-(2- methory4-hydroacymethylphenyl) ether Ethylene-bis- (2- methoxy 4 hydroxymethylphenyl) ether washeated 1 h0ur at a temperature of 1'75-196 C. During the heating there was active boiling as water was split out during the condensation. The product was a low-melting, colorless, resinous solid. It was'insoluble in most solvents but could be dissolved in dimethyl tormamide. y

A 25% solution of the-product of Example '7 in dimethyl formamide and'cont'aining 1% oxalic acid was coated on a steel rod, dried in an oven at 110 C., and then baked for 1 hours at 160- 170 C. Four successive coatings were applied in this manner. The film was transparent and had a light amber color. It was resistant to all organic solvents and v'lith'st'ood 6 hours'boiling in 9% sulfuric acid.

Example 10.-Cohdensation pf ethylehe-bis-(Z- methory--hydrozcymethplp'henyl) ether to a molding compound Five parts or the of "Example was dissolved in 380 parts of boiling water, and 3 parts of hydrochloric acid as added. The mixture was stirred at refluxing temperature for 2 hours.

The mixture became cloudy and an oil separated which gradually solidified. The product was removed by filtration. It was a thermoplastic mixture which softened at 50 C.

E rample 1 1.MOZding Three grams of the product described in Example was placed in a cylindrical stainless steel mold having a cross-sectional area of 0.787 sq. in. The mold was heated to 200 C. over a period of 40 minutes, and a pressure of 8345 pounds per sq. in. was applied. The mold was allowed to cool under pressure. The product was a clear, almost colorless molded disk which would take a high polish and could be easily machined. It was insoluble in all organic solvents and resisted the action of mineral acids. It was completely infusible.

Example 12.-C0hdensation of tetramethylenebis (2 methomy 4 hydroxymethylphenyl) ether The product of Example 6 was heated 2 hours at 175-250 C. The molten material boiled during the heating and became progressively more viscous. On cooling, a hard glassy resin remained. A small amount of this material was dissolved in dimethyl formamide and coated on a glass plate. It was dried in an oven at 115 C. and then heated for one hour at 130 C. The product did not melt below 300 C. and was resistant to 10% sulfuric acid at 100 C.

Example 13.-Condensation of bis-(Z-methoazy- 4-hydroxymethylphenoxyethyl) ether The product of Example '7 was heated at 180-220 C. for 3 hours. A hard glassy solid was obtained on cooling. The product was dissolved in dimethyl formamide and a trace of oxalic acid was added. The solution was coated on a glass plate and dried two hours at 120 C. followed by baking 30 minutes under an infra- ".6 red lamp. The resulting film was hard and resistant to 10% sulfuric acid 1 at C. It softened at 100 C. but did not melt below 300 C.

Example 1-4.-Ethylene di-ethylvam'llin ether OCnHt 021 50 A mixture of 4155 parts of 'ethy-lvanillin, 10

C. The product was ethylene di-ethylvanillin ether.

Example 15 EthilJZehe bis- (2 ethomy 4 71471-- dro'xymethylphenyl) ether OC2H5 02H? Go omomo-Qommr A mixture of 25 parts of ethylene di-ethyl-, vanillin ether, 365 parts of methyl isobutyl carbinol and 9.5 parts of aluminum isopropoxide was placed in the apparatus described in Example 5 and the distillation was carried out as described there until all the methyl isobutyl ketone that was formed had been'removed. The excess methyl isobutyl carbinol was removed by steam distillation. The residue was crystallized from water. The product melted at 117-118 C.

Example 16.-C'ohdensation of ethyZene-bis-(Z- ethory-4-hydroazymethylphenyl) ether Two parts of ethylene-bis-(2-ethoxy-4-hydroxymethylphenyl) ether was dissolved in parts of hot water containing 1.3 parts of hydrochloric acid. The mixture was refluxed and it became cloudy at once. After 2% hours of refluxing a resin had separated and was removed. This resin softened at 50 C. It was ground to a powder and molded in a press at 200 C. and a pressure of 6000 lbs. per sq. in. A tough disk of light color was obtained. It did not melt at 300 C.

The products of this invention are useful for the formation of films and molded objects. They are particularly useful where the products must withstand high temperatures or acid conditions.

The dihydric alcohols and the dialdehydes described in this application are claimed in divisional applications Serial Nos. 353,670 and 353,671, respectively, filed May '7, 1953.

We claim:

1. The resinous condensation products obtained by heating dihydric alcohols having the formula OR; R10 msgosngcm wherein R represents one of the divalent aliphatic groups consisting of CH2CH2-, CH2CH2CH2-, -CH2CH2CH2CH2 and -CH2-CH2-OCH2CH2-, and R1 represents a radical of the group consisting of methyl and ethyl.

' 2; rh'pf e ss 'arfp ep 'rmg infusible resins from compounds having the formula wherein R represents one of the divalent aliphatic groups consisting of CH2CH2, CHz-CH2 CH2-, CH2CH2-CH2CH2 and -CH2CH2--O CHz-CH2, and R1 represents a radical of, the group consisting of :methyl and ethyl which comprises heating the compounds at a temperature in the range of 3. The resinous condensation products obtained by heating dihydric alcohols having the .formula V OCH: CHzO wherein R represents one of the divalent aliphatic groups consisting of -CH2CH2, CH2CH2-CH2-, --CH2-CH2CH2-CH2 and CHzCH2OCH2-CH2-.

4. The process of preparing infusible resins from compounds having the formula (|)CHa CHaO wherein R represents one of the divalent aliphatic groups consisting of CH2CH2-, -CH2CH2CH2-, -CH2CH2CH2CH2 and -CH2CH2OCH2-CH2- which momon CHzOH prises heating'the compounds at a temperature in the range of -200 C.

5. The resinous condensation product obtained by heating to a temperature of from 130-200 C. the compound OCHs CHaO HOCHPGOCHQCEHOOOHMH 6. The infusible colorless molded condensation product of compounds having the formula wherein R represents one of the divalent aliphatic groups consisting of CH2CH2-, -CH2CH2-CH2, CH2CH2CH2CH2-, and CH2CH2-OCH2CH2, and R1 represents a radical of the group consisting of methyl and ethyl.

LOUIS H. BOCK.

LEWIS J. CARLSON.

References Cited in the file of this patent 

1. THE RESINOUS CONDENSATION PRODUCTS OBTAINED BY HEATING DIHYDRIC ALCOHOLS HAVING THE FORMULA 